Tetrahedral tetraphosphonic acids. New building blocks in supramolecular chemistry

Article abstract of DOI:10.1021/acs.cgd.5b00811

The structural characterization of tetraphenylmethane tetrakis-4-phosphonic acid (4a) and its closely related Si-analogue tetraphenylsilane tetrakis-4-phosphonic acid (4b) is reported. Crystals of 4a, obtained by crystallization at 165 °C from water under hydrothermal conditions, comprise a dense threefold interpenetrated hydrogen-bonded network. Lower calculated density cocrystals 4b·4 EtOH, attained by recrystallization from ethanol, give rise to a porous honeycomb network that shows no interpenetration. Isolated from the mother liquor, the encapsulated ethanol is rapidly lost under ambient conditions leaving amorphous 4b. While the amorphous 4b is reasonably soluble in methanol, crystalline 4a is virtually insoluble in common organic solvents.

Full text of DOI:10.1021/acs.cgd.5b00811

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Article
Tetrahedral Tetraphosphonic Acids. New
Building Blocks in SupramolecularChemistry
Alexandra Schütrumpf, Erdo#an Kirpi, Aysun Bulut, Flavien L. Morel, Marco Ranocchiari,
Enno Lork, Yunus Zorlu, Simon Grabowsky, Gündo# Yücesan, and Jens Beckmann
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00811 • Publication Date (Web): 21 Aug 2015
Downloaded from http://pubs.acs.org on August 23, 2015
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Tetrahedral Tetraphosphonic Acids. New Building Blocks in Supramolecular Chemistry
Alexandra Schütrumpf,a Erdoğan Kirpi,b Aysun Bulut,c Flavien L. Morel,d Marco
Ranocchiari,e Enno Lork,a Yunus Zorlu,f Simon Grabowsky,a Gündoğ Yücesan,g* Jens
Beckmanna*
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a Institut für Anorganische Chemie und Kristallographie, Universität Bremen, Leobener Straße, 28359 Bremen,
Germany.
b Department of Chemistry, Yildiz Technical University, Davutpasa Campus, Esenler, 34010 Istanbul, Turkey.
c Bölümü, Davutpaꢀa Cad. No.127, 34210 Esenler, Đstanbul, Turkey.
d Department of Chemistry and Applied Biosciences, ETH Zürich, VladimirꢁPrelogꢁWeg 1, 8093 Zürich,
Switzerland.
e Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institut, 5232 Villigen, Switzerland.
f Gebze Technical University, Department of Chemistry, P. O. Box 141 Gebze, 41400 Kocaeli, Turkey.
g Yıldız Technical Üniversitesi Davutpaꢀa Kampüsü, KimyaꢁMetalürji Fakültesi, Biyomühendislik, Turkey.
Received
Abstract
The structural characterization of tetraphenylmethane tetrakisꢀ4ꢀphosphonic acid (4a) and its
closely related Siꢀanalogue tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid (4b) is reported.
Crystals of 4a, obtained by crystallization at 165°C from water under hydrothermal
conditions, comprise a dense threeꢀfold interpenetrated hydrogenꢀbonded network. Lower
calculated density coꢀcrystals 4b·4 EtOH, attained by recrystallization from ethanol, give rise
* Correspondence to Jens Beckmann (Eꢀmail: j.beckmann@uniꢀbremen.de) and Gündoğ Yücesan (Eꢀmail:
gyucesan@yildiz.edu.tr)
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to a porous honeycomb network that shows no interpenetration. Isolated from the mother
liquor the encapsulated ethanol is rapidly lost under ambient conditions leaving amorphous
4b. While the amorphous 4b is reasonably soluble in methanol, crystalline 4a is virtually
insoluble in common organic solvents.
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Introduction
The construction of porous materials such as MOFs and COFs requires the judicious choice of
rigid building blocks that contain functional groups suitable for metal coordination to form the
desired organicꢀinorganic hybrid framework.1ꢀ4 Particularly trigonal planar aromatic
carboxylates provide structural rigidity and controllable design elements to produce
isoreticular expansions with wellꢀestablished secondary building units.5ꢀ8 Most of the aromatic
carboxylates with suitable sizes for MOF synthesis has been exploited to reach the optimum
surface areas and gas adsorption properties. Although all these efforts to produce carboxylateꢀ
based MOFs have provided valuable insight into coordination chemistry, alternative bridging
ligands with wider selection of adhesive functional groups such as, phosphonates9ꢀ12 and
arsenates13 have been vastly neglected. The expansion of MOF research into different
functional groups is required not only to produce novel MOFs with improved properties but
also to address stability issues. Metalꢀorganophosphonates form a wellꢀknown class of hybrid
frameworks possessing wide range of applications including sorption, separation, optics and
catalysis.14ꢀ16 But their synthesis has been limited mostly to aliphatic diphoshonic acids and a
comparatively few aromatic phosphonic acids.17ꢀ47 Prominent examples include the trigonal
building blocks 1,3,5ꢀbenzene tri(phosphonic acid),34ꢀ40 1,3,5ꢀbenzene tri(pꢀphenylphosphonic
acid),41ꢀ45 1,3,5ꢀtriazine tri(phosphonic acid)46 and 1,3,5ꢀtriazine tri(pꢀphenylphosphonic
acid).47 Phosphonates have tetrahedral RPO32– structure with three oxygen atoms available for
metal binding. The rich coordination modes of tetrahedral phosphonates on metal centers are
expected to produce many new secondary building units with different transition elements.48
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On the other hand, tetraphosphonates have multiple modes of tunable negative charges
between 0 and ꢀ8, which is dependent on the reaction pH conditions. Therefore, they could
initiate the formation of interesting metal oxidation states and novel metal clusters to balance
the negative charges especially with transition metals possessing multiple oxidation states
such as, vanadium, manganese and molybdenum etc. All these charge balance efforts could
result in pH controlled tunable coordination chemistry producing interesting magnetic and
catalytic properties.49ꢀ52 MOFs constructed using the aromatic tetrahedral ligands are among
the ones producing the highest porosities.53ꢀ56 This is mostly due to the fact that the tetrahedral
ligands open into threeꢀdimensions with an angle of 109 degrees at the center of the ligand
forming four trigonal pyramidal domes (Chart 1).
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Chart 1.
Tetrahedral building blocks based on tetraphenylmethane and ꢀsilane
As the threeꢀdimensional metal organic framework forms, these pyramidal domes are
expected to expand into threeꢀdimensional networks via metal centers to form the full
cavities. The hydrophobic tetrahedral center is surrounded by hydrophilic adhesive functional
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groups providing that no metal oxides can penetrate into the tetrahedral cavities increasing the
chances of obtaining void spaces.57ꢀ60 On the other hand, planar aromatic ligands like 1,4ꢀ
phenyldiphosphonic and 4,4’ꢀbiphenyldiphosphonic acids require special coordination modes
on metal centers and solvent requirements to avoid πꢀstacking and pillaredꢀlayered
organizations to form void spaces.52 All these information suggests that when synthesized,
tetrahedral phosphonate ligands would be very interesting linkers to produce more robust
metal phosphonate frameworks providing diverse functions. Several tetrahedral building
blocks based on tetraphenylmethane and ꢀsilane with different adhesive functional groups
have already been reported already, which involve the carboxylic acids 1a and 1b,61ꢀ65 the
boronic acids 2a and 2b,66 the silanols 3a and 3b67 and the sulfonic acid 4a68 (Chart 1). We
were interested to prepare the related arylphosphonic acids 5a and 5b to use them as building
blocks in supramolecular chemistry. During the course of our work, the synthesis of
tetraphenylmethane tetrakisꢀ4ꢀphosphonic acid (5a) was already reported by Zaręba and Zoń
et al. In the same paper, the authors described crystals structures of corresponding pyridinium
and ammonium phosphonates, however, no structural data of the free acid 5a were
disclosed.69 Here we describe the synthesis of tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid
(5b) as well as the molecular and crystal structures of 5a and 5b.
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Results and Discussion
The tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid (5b) was prepared similarly as
tetraphenylmethane tetrakisꢀ4ꢀphosphonic acid (5a)69 in two synthetic steps starting from
readily available tetrakis(4ꢀbromophenyl)silane (4ꢀBrC6H4)4Si. The first step involves the
Pd(0) catalyzed variation of the Arbuzov reaction using triisopropylphosphite as substrate. In
this way, tetraphenylsilane tetrakis(4ꢀdiisopropyl phosphonate) (6b) was obtained after a
chromatographic workꢀup and recrystallization in 35% yield as colorless highꢀmelting crystals
(Scheme 1). The liberation of the acid 5b was achieved by the reaction of 6b with conc.
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hydrochloric acid. This simple acidic hydrolysis avoids the costly trimethylbromosilane,
which has been used by Zaręba and Zoń et al.69 Notably, the acidic hydrolysis procedure
works also for 5a. After recrystallisation from ethanol, 5a and 5b were obtained as ethanol
solvates in 98% and 89% yield, respectively. Once isolated from the mother liquor the ethanol
was rapidly lost leaving only amorphous materials.
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Scheme 1.
Synthesis of tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid (5b)
However, when covered by oil single crystals of 5b·EtOH suitable for Xꢀray crystallography
were obtained. High quality single crystals of 5a were obtained in the form of rectangular
plates by crystallization under hydrothermal conditions (165°C, autogeneous pressure) from
water. Replacing the water by DMF using the same method between 150 and 200 °C
produced the same crystals of 5a. Under high pressure and temperature, the density of the
crystals is anticipated to be higher. Consistently, the calculated density of 5a (1.615 g cm–3) is
much higher than of 5b (1.304 g cm–3), respectively. The molecular structures of 5a and 5b·4
EtOH and a superimposed stick model are shown in Figure 1. The molecular structure of 6b is
shown in the ESI (Figure S1). Tetrahedral central atoms are only slightly distorted, which is
reflected in CꢀCꢀC angles of 5a (103.9(3)° and 112.3(2)°) and CꢀSiꢀC angles of 5b (106.5(4)°
and 111.0(2)° that differ only marginally from the ideal tetrahedral angle.
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Figure 1.
Molecular structures of 5a (left) and 5b·4 EtOH (middle) showing 30%
probability ellipsoids and the crystallographic numbering scheme as well as superimposed
stick models of 5a and 5b (right).
Together with the high rigidity of the phenyl rings both molecules possess very little
conformational flexibility and consequently the molecular structure are very similar. Minor
differences were observed in the alignment of the phenyl groups. In the crystal lattice
individual molecules are associated by hydrogen bonding, which involves also of the solvated
ethanol. The hydrogenꢀbond motifs of 5a (left) and 5b·4 EtOH are shown in Figure 2.
Figure 2.
Hydrogenꢀbond motifs of 5a (left) and 5b·4 EtOH (right).
In 5a, four phosphonate groups comprise a finite, 3D cageꢀlike hydrogenꢀbonded network,
whereas in 5b·4 EtOH, a rather 2D infinite network propagates through the crystal lattice.
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Both hydrogenꢀbonded motifs contain cyclic subunits that can be classified by the ternary
graph set ꢀꢁꢁ(10).70 In all phosphonic acid moieties, the P=O groups accept two hydrogen
atoms of OH groups giving to rise to bifurcated hydrogenꢀbridges typical for phosphonic
acids.71 While the PꢀOH groups act only as hydrogen bond donors, the ethanol molecules
serves as both donor and acceptor of the hydrogen bridge. The short donorꢀacceptor distances
of 5a (O3a···O1c 2.579(5) Å) and 5b·4 EtOH (O3a···O4a 2.538(1) Å, O2···O1a 2.563(1) Å)
are indicative for strong hydrogen bonds and cooperativity.71,72 Notably, in 5b·4 EtOH there
is also a weaker hydrogen bridge as evidenced by a longer donorꢀacceptor distances
(O4a···O1 2.702(1) Å). In order to evaluate the importance of these hydrogen bonds for the
crystal packing compared to other intermolecular forces, a Hirshfeld surface analysis was
carried out. A Hirshfeld Surface (HS)73 is the outer contour of the space which a molecule or
an atom consumes in a crystalline environment. It can be compared to the van der Waals
envelope which other molecules or atoms come into contact with when interactions are
present. The directions and strengths of these interactions can be mapped onto the HSs using
various descriptors such as dnorm.74 This is a ratio encompassing the distances of any surface
point to the nearby interior (di) and exterior atoms (de) and the van der Waals radii of the
atoms.74 Red colored regions in Figure 3a,b (i.e. negative values of dnorm) as well as flattened
regions of the HS itself locally indicate the existence of close contacts. For both 5a and 5b, all
of these contacts can be identified as classical hydrogen bonds. No other type of interaction is
structurally directing according to the HS representations. Fingerprint plots75 are a 2ꢀ
dimensional projection of the dnormꢀmapped HSs visualising contacts as diꢀde data points. Each
data point represents the sum of the closest distances from any point on the HS to an internal
and external atom, which can vary in length. Shortest contacts appear with distinct features
such as spikes for OꢁꢁꢁH hydrogen bonds or peripheral spikes for CꢀHꢁꢁꢁπ interactions, see
Figures 3c,d.
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(a)
(b)
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(c)
(d)
Figure 3.
Hirshfeld Surfaces with dnorm mapped onto them for 5a (a) and 5b ꢁ4 EtOH (b).
Colour code = –0.821 (red ) to 1.691 (blue). Fingerprint plots for 5a (c) and 5b ꢁ4 EtOH (d)
showing distinct features for characteristic short contacts (such as spikes) together with the
overall percentage contribution of a contact type to the crystal packing. All pictures generated
with the program CrystalExplorer.76
As an additional piece of information, the total percentage contribution of each contact type to
the crystal packing is added to these Figures. Both compounds have very similar fingerprint
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plots, dominated by hydrogen bonding in terms of both the characteristic spikes and the total
contribution (46.6% for 5a, 44.9% for 5b). Dispersive HꢁꢁꢁH contacts follow in terms of the
contributions (32.5% for 5a, 35.2% for 5b). In contrast CꢁꢁꢁH contacts that represent CꢀHꢁꢁꢁπ
interactions are neither dominant in terms of the features and the contributions (14.8% and
16.8%). All other contact types (CꢁꢁꢁO, CꢁꢁꢁC, OꢁꢁꢁO) are below 5%. More detailed fingerprint
information is given in the Supporting information. As anticipated from the very different
calculated densities, the crystal structures of 5a and 5b·4 EtOH are also significantly
different. The topological analysis unraveling the connectivity patterns of the hydrogen
bonded networks are shown in Figure 4.
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Figure 4.
(a) View of the 3ꢀfold interpenetrating hydrogen bonded networks of 5a. The
three networks are presented in green, blue, and red. (b) View of the single 3D hydrogen
bonded network of 5b.
The simplified network of 5a comprises a threeꢀfold interpenetrating array similarly as
present in textile fabrics, whereas 5b possess honeycomb porous networks without any
interpenetration.77ꢀ79 The inside of these pores is filled by the ethyl groups of the solvated
ethanol. The high volatility of the ethanol upon isolation from the mother liquor raises the
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question the stability of the remaining network and the void space. Calculation of the void
space of 5b·4 EtOH using the crystal data and Crystal Explorer76 (iso value 0.0003) reveals
that only 1.5% of the cell volume was accessible by small gas molecules.80 Under the
assumption that the remaining network stayed intact, the ethanol was hypothetically removed
from the crystal data (by deleting the coordinates from the cif file). In this case the assessable
void space increased to 28.4%. To verify the validity of the assumption a bulk sample of 5b·4
EtOH was dried in high vacuum at room temperature until the weight was constant. The
amorphous sample obtained, hereafter referred to as 5b, remains soluble in methanol. This
noteworthy as crystals of 5a prepared under hydrothermal conditions are virtually insoluble,
presumably due the high lattice energy associated with the threeꢀfold interpenetrating
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network. The 31P NMR spectrum (D4ꢀmethanol) of 5b shows a single resonance at
δ = 16.5
ppm. Consistent with the loss of crystallinity, an Xꢀray powder diffractogram exhibits no
reflections for 5b, which suggests that the remaining hydrogenꢀbonded network collapsed
when the ethanol was removed. This was also confirmed by measuring the BET surface area,
which showed virtually no N2 physisorption of 5b at 77K. The amorphous 5b was further
characterized by 31P MAS NMR spectroscopy and DTA analysis. The 31P MAS NMR
spectrum of 5b shows a main signal at
18.5 and 0.2 ppm (see ESI for the spectrum). The number of signals is attributed to the
different local environments of the phosphorous atoms. The signals at iso = 24.5 and 18.5
ppm were tentatively assigned to phosphonate groups being involved in different hydrogenꢀ
bond motifs. The signal at iso = 38.2 might be due to a phosphonate group in which one or
both OH groups are notꢀhydrogen bonded. The small signal at iso = 0.2 ppm might even
δiso = 24.5 ppm and minor intense signals at δiso = 38.2,
δ
δ
δ
belong to phosphonate that underwent condensation (see below). The DTA analysis shows
mass loss of about 10% up to 300°C, most likely water that formed during the condensation
of phosphonate groups. When a bulk sample of 5b was heated for 14 h at 280°C, a colourless
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amorphous sample, hereafter named 5b' was obtained and water was detected in the cooling
trap. In contrast to 5b, the heated sample 5b' was virtually insoluble in methanol or other
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solvents. The 31P MAS NMR spectrum of 5b' gave rise to a main signal at
δiso = –1.3 ppm and
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two minor intense signals at 6.5 and –12.6 ppm. The poor solubility and the highꢀfield shift of
the 31P MAS NMR resonances suggest that the (partial) condensation of PꢀOH groups into Pꢀ
OꢀP linkages took place. Measurement of the BET surface area confirmed that 5b' also lacks
any porosity. The DTA analysis of 5b above 300°C indicates complete thermal degradation of
the material in two mass loss incidents from 300 to 550°C (40%) and from 550 to 800°C
(20%).
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Conclusions
Besides the very recently reported tetraphenylmethane tetrakisꢀ4ꢀphosphonic acid (5a),69 the
closely related Siꢀanalogue tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid (5b) was prepared in
two synthetic steps. Although the molecular structures of 5a and 5b are very similar, the
crystal structures are significantly different, which can be related to the way the crystals were
grown. Highly dense crystals of 5a were obtained by crystallization from water at 165°C
under hydrothermal conditions. The crystal structure of 5a features a threeꢀfolded hydrogenꢀ
bonded network, which explains the virtual insolubility in methanol and other organic
solvents. Recrystallization from ethanol under normal pressure afforded lower density coꢀ
crystals with the solvent, 5b·4 EtOH, the crystal structure of which reveals a porous
honeycomb network that lacks interpenetration. Once isolated from the mother liquor, the
ethanol molecules, situated partly in the voids defuse out of the crystal lattice leaving
amorphous 5b still being soluble in methanol. Heating 5b at temperatures nearly 300°C
proceeds with condensation of the PꢀOH groups to give an insoluble crossꢀlinked material
with PꢀOꢀP linkages. Due to conformational rigidity, 5a and 5b hold great potential as
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tetrahedral building blocks for the preparation of metal organic frameworks (MOFs), which is
actively being pursued in our laboratories.
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Supporting Information
Crystallographic data files in CIF format, experimental procedures, crystal and refinement
details, Fingerprints for the separate intermolecular forces, thermogravimetric analysis, solidꢀ
state 31P NMR spectroscopy, Nitrogen physisorption, additional references. This material is
available free of charge via the internet at http://pubs.acs.org.
Author Information
Corresponding Authors
* J.B. Eꢀmail: j.beckmann@uniꢀbremen.de)
* G.Y. Eꢀmail: gyucesan@yildiz.edu.tr
Notes
The authors declare no competing financial interest
Acknowledgement
Financial support by the Deutsche Forschungsgemeinschaft (DFG) within the Emmy Noether
scheme GR4451/1ꢀ1 and the Türkiye Bilimsel ve Teknolojik Araꢂtırma Kurumu (TÜBĐTAK
212T060) is gratefully acknowledged.
Dedication
Dedicated to Professor Derek Woollins on the occasion of his 60th birthday
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2
3
References
4
5
6
7
8
[1]
Desiraju, G. R. In Crystal Engineering: The Design of Organic Solids; Elsevier:
Amsterdam, 1989.
9
[2]
[3]
Vögtle, F. In Supramolecular Chemistry; Wiley: Chichester, 1991.
Lehn, J.ꢀM. In Supramolecular Chemistry: Concepts and Perspectives; VCH: New
York, 1995.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[4]
[5]
[6]
[7]
[8]
[9]
Lehn, J.ꢀM. In Comprehensive Supramolecular Chemistry; Pergamon: New York,
1996.
Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. Science 2013, 341, 974ꢀ
988.
Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. Ö.;
Snurr, R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M. Science 2010, 329, 424ꢀ428.
Guillerm, V.; Kim, D.; Eubank, J. F.; Luebke, R.; Liu, X.; Adil, K.; Lah, M. S.;
Eddaoudi, M. Chem. Soc. Rev., 2014, 43, 6141ꢀ6172 and references therein.
Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J.
Nature 2003, 423, 705ꢀ714.
Clearfield, A. In Design of New Materials; eds. Cocke, D. L., Clearfield, A. Plenum:
New York, 1986; p 121.
[10]
[11]
Clearfield, A. Solvent Extr. Ion Exch., 2000, 18, 655ꢀ678.
Byrd, H.; Clearfield, A.; Poojay, D. M.; Reis, K. P.; Thompson, M. E. Chem. Mater.
1996, 8, 2239ꢀ2246.
[12]
[13]
Konar, S.; Zoñ, J.; Prosvirin, A. V.; Dunbar, K. R.; Clearfield, A. Inorg. Chem. 2007,
46, 5229ꢀ5236 and references therein.
Burkholder, E.; Wright, S.; Golub, V.; O’Connor, C. J.; Zubieta, J. Inorg. Chem.
2003, 42, 7460ꢀ7471.
13
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Crystal Growth & Design
Page 14 of 18
1
2
3
4
5
6
7
8
9
[14]
[15]
Kevin J.; Gagnon, K. J.; Perry, H. P.; Clearfield, A. Chem. Rev. 2012, 112, 1034ꢀ
1054.
Luebke, R.; Weseliński, L. J.; Belmabkhout, Y.; Chen, Z.; Wojtas, Ł.; Eddaoudi, M.
Cryst. Growth Des. 2014, 14, 414ꢀ418.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[16]
[17]
[18]
Yiing, S.ꢀM.; Mao, J.ꢀG. Cryst. Growth Des. 2006, 6, 964ꢀ968.
Clearfield, A.; Wang, Z. J. Chem. Soc., Dalton Trans. 2002, 2937ꢀ2947.
Finn, R. C.; Zubieta, J.; Haushalter, R. C. Crystal Chemistry of Organically
Templated Vanadium Phosphates and Organophosphonates; John Wiley & Sons,
Inc.: New York, 2003; p 421.
[19]
Fu, R.ꢀB.; Wu, X.ꢀT.; Hu, S.ꢀM.; Zhang, J.ꢀJ.; Fu, Z.ꢀY.; Du, W.ꢀX. Polyhedron
2003, 22, 2739ꢀ2744.
[20]
[21]
[22]
Merrill, C. A.; Cheetham, A. K. Inorg. Chem. 2005, 44, 5273ꢀ5277.
Merrill, C. A.; Cheetham, A. K. Inorg. Chem. 2007, 46, 278ꢀ284.
Ouellette, W.; Yu, M. H.; O’Connor, C. J.; Zubieta, J. Inorg. Chem. 2006, 45, 3224ꢀ
3229.
[23]
Ouellette, W.; Yu, M. H.; O’Connor, C. J.; Zubieta, J. Inorg. Chem. 2006, 45, 7628ꢀ
7641.
[24]
[25]
Yücesan, G.; Golub, V.; O’Connor C. J.; Zubieta, J. Dalton Trans. 2005, 2241ꢀ2251.
Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem. Soc. Rev., 2009, 38,
1430ꢀ1449.
[26]
[27]
[28]
[29]
Clearfield, A. Curr. Opin. Solid State Mater. Sci. 1996, 1, 268ꢀ278.
Clearfield, A. Curr. Opin. Solid State Mater. Sci. 2002, 6, 495ꢀ506.
Clearfield, A.; Wang, Z. J. Chem. Soc., Dalton Trans. 2002, 2937ꢀ2047.
Vioux, A.; Le Bideau, J.; Mutin, P. H.; Leclercq, D. Top. Curr. Chem. 2004, 232,
145ꢀ174.
[30]
Maeda, K. Micropor. Mesopor. Mat. 2004, 73, 47ꢀ55.
14
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Page 15 of 18
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
[31]
[32]
[33]
Mosby, B. M.; Díaz, A.; Clearfield, A. Dalton Trans., 2014, 43, 10328ꢀ10339.
Białek, M. J.; Janczak, J.; Zoñ, J. CrystEngComm, 2013, 15, 390ꢀ399.
Białek, M. J.; Zaręba, J. K.; Janczak J.; Zoñ, J. Cryst. Growth Des. 2013, 13, 4039ꢀ
4050.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[34]
[35]
[36]
[37]
Mehring, M. Eur. J. Inorg. Chem. 2004, 3240ꢀ3246.
Kong, D. ; Clearfield, A. ; Zoń, J. Crystal Growth Des. 2005, 5, 1767ꢀ1773.
Kong, D.; Zoñ, J.; McBee, J.; Clearfield, A. Inorg. Chem. 2006, 45, 977ꢀ986.
Hix, G. B. ; Caignaert, V. ; Rueff, J.ꢀM.; Le Pluart, L. ; Warren, J. E. ; Jaffrès, P.ꢀA.
Crystal Growth Des. 2007, 7, 208ꢀ211.
[38]
[39]
Kong, D. ; Clearfield, A. ; Zoñ, J. Crystal Growth Des. 2008, 8, 2892ꢀ2898.
Taylor, J. M. ; Mah, R. K. ; Moudrakovski, I. L. ; Ratcliffe, C. I. ; Vaidhyanathan,
R. ; Shimizu, G. K. H. J. Am. Chem. Soc. 2010, 132, 14055ꢀ14057.
Pramanik, M. ; Bhaumik, A. Chem. Eur. J. 2013, 19, 8507ꢀ8514.
Beckmann, J.; Rüttinger, R.; Schwich, T. Cryst. Growth Des. 2008, 8, 3271ꢀ3276.
Vaidhyanathan, R. ; Mahmoudkhani, A. H. ; Shimizu, G. K. H. Can. J. Chem. 2009,
87, 247ꢀ253.
[40]
[41]
[42]
[43]
Ouellette, W.; Wang, G.; Liu, H.; Yee, G. T.; O’Connor, C. J.; Zubieta, J. Inorg.
Chem. 2009, 48, 953ꢀ963.
[44]
[45]
Mah, R. K.; Lui, M. W.; Shimizu, G. K. H. Inorg. Chem. 2013, 52, 7311ꢀ7313.
Taddei, M.; Costantino, F.; Vivani, R.; Sabatini, S.; Lim, S.ꢀH. Cohen, S. M. Chem.
Commun. 2014, 50, 5737ꢀ5740.
[46]
Maxim, C. ; Matni, A. ; Geoffroy, M. ; Andruh, M.; Hearns, N.G.R. Clérac, R. ;
Avarvari, N. New J. Chem. 2010, 34, 2319ꢀ2327.
[47]
[48]
Hermer, N.; Stock, N. Dalton Trans. 2015, 44, 3720ꢀ3723.
Sahoo, D.; Suriyanarayanan, R.; Chandrasekhar V. Dalton Trans. 2014, 43, 10898ꢀ
10909.
15
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Crystal Growth & Design
Page 16 of 18
1
2
3
4
5
6
7
8
9
[49]
[50]
[51]
[52]
Meada, K. Micropor. Mesopor. Mat. 2004, 73, 47ꢀ55.
Du, Z.ꢀY.; Xu, H.ꢀB.; Mao, J.ꢀG. Inorg. Chem. 2006, 45, 6424ꢀ6430.
Kahn, O. Molecular Magnetizm; VCH:New York, 1993.
Clearfield, A.; Demadis K. Metal Phosphonate Chemistry: From Synthesis to
Applications; RSC Publishing:Cambridge, 2012.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[53]
Zhang, Y.ꢀB.; Su, J.; Furukawa, H.; Yun, Y.; Gándara, F.; Duong, A.; Zou, X.;
Yaghi, O. M. J. Am. Chem. Soc. 2013, 135, 16336ꢀ16339.
Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M. Chem. Rev. 2014, 114, 1343ꢀ1370.
Dinca, M.; Dailly, A.; Long, J. R. Chem. Eur. J. 2008, 14, 10280ꢀ10285.
Ren; H.; Ben, T.; Wang, E.; Jing, X.; Xue, M.; Liu, B.; Cui, Y.; Qiua, S.; Zhu, G.
Chem. Commun. 2010, 46, 291ꢀ293.
[54]
[55]
[56]
[57]
[58]
Vasylyev, M.; Neumann, R. Chem. Mater. 2006, 18, 2781ꢀ2783.
Vasylyev, M.; Wachtel, E. J.; PopovitzꢀBiro, R.; Neumann, R. Chem. Eur. J. 2006,
12, 3507ꢀ3514.
[59]
[60]
Taylor, J. M.; Mahmoudkhani, A. H.; Shimizu, G. K. H. Angew. Chem. Int. Ed.
2007, 46, 795ꢀ798.
Jones, K. M. E.; Mahmoudkhani, A. H.; Chandler, B. D.; Shimizu, G. K. H.
CrystEngComm 2006, 8, 303ꢀ305.
[61]
[62]
Lambert, J. B.; Liu, Z.; Liu, C. Organometallics 2008, 27, 1464ꢀ1469.
Davies, R. P.; Less, R. J.; Lickiss, P. D.; Robertson, K; White, A. J.; P. Inorg. Chem.
2008, 47, 9958ꢀ9964.
[63]
[64]
Davies, R. P.; Less, R.; Lickiss, P. D.; Robertson, K.; White, A. J. P.
Organometallics 2010, 10, 4571ꢀ4581.
Mandic, S.; Healey, M. R.; Gotthardt, J. M.; Alley, K. G. Gable, R. W.; Ritchie, C.;
Boskovic, C. Eur. J. Inorg. Chem. 2013, 1631ꢀ1634.
16
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Page 17 of 18
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
[65]
[66]
[67]
Lee, J. H.; Moon, B.; Kim, T. K.; Jeoung, S.; Moon, H. R. Dalton Trans. 2015, DOI:
10.1039/C5DT00690B.
Fournier, J.ꢀH.; Maris, T., Wuest, J. D.; Guo, W.; Galoppini, E. J. Amer. Chem. Soc.
2003, 125, 1002ꢀ1006.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Kawakami, Y.; Sakuma, Y.; Wakuda, T.; Nakai, T.; Shirasaka, M.; Kabe, Y.
Organometallics 2010, 29, 3281ꢀ3288.
[68]
[69]
Sarma, B.; Nangia, A. CrystEngComm. 2007, 9, 628ꢀ631.
Zareba, J. K.; Bialek, M. J.; Janczak, J.; Zoñ, J.; Dobosz, A. Crystal Growth
Des. 2014, 14, 6143ꢀ6153.
[70]
Bernstein, J.; Davies, R. E.; Shimoni, L.; Chang, N.ꢀL. Angew. Chem. Int. Ed. 1995,
34, 1555ꢀ1573.
[71]
[72]
[73]
[74]
[75]
[76]
Mehring, M.; Schürmann, M.; Ludwig, R. Chem. Eur. J. 2003, 9, 838ꢀ849.
Steiner, T. Angew. Chem. Int. Ed. 2002, 41, 49ꢀ76.
Spackman, M. A.; Byrom, P. G. Chem. Phys. Lett., 1997, 267, 215ꢀ220.
McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. Chem. Commun. 2007, 3814ꢀ3816.
Spackman, M. A.; McKinnon, J. J. CrystEngComm. 2002, 4, 378ꢀ392.
CrystalExplorer (Version 3.1), Wolff, S.K.; Grimwood, D.J.; McKinnon, J.J.; Turner,
M.J.; Jayatilaka, D.; Spackman, M.A. University of Western Australia, 2012.
Blatov, V. A. TOPOS 4.0 Professional, Commission on Crystallographic Computing,
IUCr, 2006.
[77]
[78]
Alexandrov, E. V.; Blatov, V. A.; Kochetkov, A. V.; Proserpio, D. M.
CrystEngComm 2011, 13, 3947ꢀ3958.
[79]
[80]
Blatov, V. A. Struct. Chem. 2012, 23, 955ꢀ963.
Turner, M. J.; McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. CrystEngComm.
2011, 13, 1804ꢀ1813.
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Tetrahedral Tetraphosphonic Acids. New Building Blocks in Supramolecular Chemistry
Alexandra Schütrumpf, Erdoğan Kirpi, Aysun Bulut, Flavien L. Morel, Marco Ranocchiari,
Enno Lork, Yunus Zorlu, Simon Grabowsky, Gündoğ Yücesan, Jens Beckmann
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Tetraphenylmethane tetrakisꢀ4ꢀphosphonic acid crystallized under hydrothermal conditions
provided a dense threeꢀfold interpenetrated hydrogenꢀbonded network, whereas the closely
related tetraphenylsilane tetrakisꢀ4ꢀphosphonic acid crystallized from ethanol to give rise to a
porous honeycomb network that shows no interpenetration.
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